Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
  • B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/56—Platinum group metals
  • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/56—Platinum group metals
  • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/56—Platinum group metals
  • B01J23/63—Platinum group metals with rare earths or actinides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
  • B01J35/391—Physical properties of the active metal ingredient
  • B01J35/393—Metal or metal oxide crystallite size
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
  • B01J35/45—Nanoparticles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/613—10-100 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
  • B01J35/77—Compounds characterised by their crystallite size
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
  • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
  • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
  • C07C5/333—Catalytic processes
  • C07C5/3335—Catalytic processes with metals
  • C07C5/3337—Catalytic processes with metals of the platinum group
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
  • B01J2235/15—X-ray diffraction
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
  • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
  • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • C07C2521/08—Silica
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
  • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
  • C07C2523/56—Platinum group metals
  • C07C2523/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
  • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
  • C07C2523/56—Platinum group metals
  • C07C2523/63—Platinum group metals with rare earths or actinides
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

• the invention relates to catalyst particles, to a process for their preparation and to the use of the catalyst particles as dehydrogenation catalyst.
• DE-A 196 54 391 describes the preparation of a dehydrogenation catalyst by impregnation of essentially monoclinic ZrO 2 with a solution of Pt (NO 3 ) 2 and Sn (OAc) 2 or by impregnation of ZrO 2 with a first solution of Pt (NO 3 ) 2 and then a second solution of La (NO 3 ) 3 .
• the impregnated carriers are dried and then calcined.
• the catalysts thus obtained are used as dehydrogenation catalysts for the dehydrogenation of propane to propene.
• the object of the present invention is to provide a cost-effective and time-saving process for the preparation of dehydrogenation catalysts, wherein the dehydrogenation catalysts obtained should be comparable in activity and selectivity to the prior art catalysts prepared by impregnation or spray-drying.
• the object is achieved by a method for producing catalyst particles comprising platinum and tin and at least one further element selected from lanthanum and cesium on a zirconia-containing carrier, comprising the steps
• (V) deposition of the particles formed from the pyrolysis gas The metal compounds and oxide-forming precursor compounds are fed to the pyrolysis zone as an aerosol. It is convenient to supply to the pyrolysis zone an aerosol which has been obtained by nebulization of only one solution containing all metal compounds and oxide-forming precursor compounds. In this way it is ensured in any case that the composition of the particles produced is homogeneous and constant.
• the individual components are therefore preferably selected such that the oxide-forming precursors present in the solution and the noble metal compounds used are present in homogeneously dissolved state until the solution is atomized.
• solution or solutions which on the one hand contain the oxide-forming precursors and, on the other hand, the active or promoter metal compounds, to be used.
• the solution or solutions may contain both polar and non-polar solvents or solvent mixtures.
• the decomposition of the noble metal compound to the noble metal and the decomposition and / or oxidation of the oxide precursors with the formation of the oxide occurs. Under certain circumstances, a part of the noble metal evaporates in order to re-deposit in colder zones on already formed carrier particles. As a result of the pyrolysis, spherical particles with varying surface area are obtained.
• the temperature in the pyrolysis zone is above the decomposition temperature of the noble metal compounds at a temperature sufficient for oxide formation, usually in the range between 500 and 2000 ° C. Preferably, the pyrolysis is carried out at a temperature of 900 to 1500 ° C.
• the pyrolysis reactor can be indirectly heated from the outside, for example by means of an electric furnace. Because of the temperature required for indirect heating From outside to inside, the furnace must be much hotter than the temperature required for pyrolysis. Indirect heating requires a temperature-stable furnace material and a complex reactor design, the required total amount of gas is, on the other hand, lower than in the case of a flame reactor.
• the pyrolysis zone is heated by a flame (flame spray pyrolysis).
• the pyrolysis zone then comprises an ignition device.
• conventional fuel gases can be used, but preferably hydrogen, methane or ethylene are used.
• the temperature can be adjusted in the pyrolysis zone targeted.
• the pyrolysis zone instead of air as the source of 0 2 for the combustion of the fuel gas and pure oxygen can be supplied.
• the total amount of gas also includes the carrier gas for the aerosol and the vaporized solvent of the aerosol.
• the one or more of the pyrolysis zone supplied aerosols are conveniently passed directly into the flame.
• the carrier gas for the aerosol While air is usually preferred as the carrier gas for the aerosol, it is also possible to use nitrogen, CO 2 , O 2 or a fuel gas, for example hydrogen, methane, ethylene, propane or butane.
• the pyrolysis zone is heated by an electrical plasma or an inductive plasma.
• the catalytically active noble metal particles precipitate on the surface of the carrier particles and are fixed firmly thereon.
• a flame spray pyrolysis device generally comprises a reservoir for the liquid to be atomized, feed lines for carrier gas, fuel gas and oxygen-containing gas, a central aerosol nozzle and an annular burner arranged around it, a device for gas-solid separation comprising a filter element and a removal device for the solid and an outlet for the exhaust gas.
• the cooling of the particles takes place by means of a quenching gas, for example nitrogen or air.
• the pyrolysis zone comprises a so-called pre-dryer, which pre-dries the aerosol before it enters the pyrolysis reactor, for example in a flow tube with a heating unit arranged around it. If pre-drying is dispensed with, there is a risk that a product with a broader grain spectrum and, in particular, too much fines will be obtained.
• the temperature of the pre-dryer depends on the nature of the dissolved precursors and their concentration. Usually, the temperature in the pre-dryer is above the boiling point of the solvent to 250 ° C; in the case of water as solvent, the temperature in the pre-dryer is preferably between 120 and 250 ° C., in particular between 150 and 200 ° C.
• the pre-dried aerosol fed via a line to the pyrolysis reactor then enters the reactor via an outlet nozzle.
• the combustion chamber which is preferably tubular, is thermally insulated.
• a pyrolysis gas containing spherical particles of varying specific surface area is obtained.
• the size distribution of the pigment particles obtained results essentially directly from the droplet spectrum of the pyrolysis zone supplied aerosol and the concentration of the solution or solutions used.
• the pyrolysis gas is cooled sufficiently before deposition of the particles formed from the pyrolysis gas so that co-sintering of the particles is excluded.
• the pyrolysis zone preferably comprises a cooling zone which adjoins the combustion chamber of the pyrolysis reactor.
• a cooling of the pyrolysis gas and the catalyst particles contained therein to a temperature of about 100-500 ° C is required, depending on the filter element used.
• a cooling to about 100 - 150 ° C instead.
• a quenching gas for example nitrogen, air or air humidified with water is introduced.
• Suitable zirconia-forming precursor compounds are alcoholates such as zirconium (IV) ethanolate, zirconium (IV) n-propoxide, zirconium (IV) isopropoxide, zirconium (IV) n-butoxide, and zirconium (IV) -tert butoxide.
• zirconium (IV) propoxide which is preferably in the form of a solution in n-propanol, is used as the ZrO 2 precursor compound.
• Suitable zirconia-forming precursor compounds are also carboxylates such as zirconium acetate, zirconium propionate, zirconium oxalate, zirconium octoate, zirconium 2-ethylhexanoate, zirconium acetate, zirconium propionate, zirconium oxalate, zirconium octanoate, zirconium 2-ethylhexanoate, zirconium neodecanoate, zirconium stearate and zirconium propionate.
• zirconium (IV) acetylacetonate is used as precursor compound.
• the precursor compounds additionally comprise a silica precursor compound.
• Suitable precursors for silicon dioxide are organosilanes and reaction products of SiCl 4 with lower alcohols or lower carboxylic acids. It is also possible to use condensates of the stated organosilanes or silanols with Si-O-Si members. Preference is given to using siloxanes. The use of Si0 2 is also possible.
• the precursor compounds comprise, as the silica-forming precursor compound, hexamethyldisiloxane.
• the catalyst particles according to the invention furthermore contain platinum and tin and at least one further element selected from lanthanum and cesium.
• the loading of Pt is 0.05 to 1% by weight and the loading of Sn is 0.05 to 2% by weight.
• Preferred precursor compounds for lanthanum or cesium are carboxylates and nitrates, for example corresponding to the carboxylates mentioned above in connection with zirconium.
• the precursor compounds comprise lanthanum (III) acetylacetonate and / or cesium acetate.
• the precursor compounds comprise lanthanum (III) 2-ethylhexanoate.
• Preferred precursor compounds for tin are carboxylates and nitrates, for example corresponding to the carboxylates mentioned above in connection with zirconium.
• the precursor compounds comprise tin 2-ethylhexanoate.
• Preferred precursor compounds for platinum are carboxylates and nitrates, for example corresponding to the carboxylates and ammonium platinates mentioned above in connection with zirconium.
• the precursor compounds comprise platinum acetylacetonate. To prepare the solution or solutions required for aerosol formation, it is possible to use both polar and apolar solvents or solvent mixtures.
• Preferred polar solvents are water, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, n-propanone, n-butanone, diethyl ether, tert-butyl methyl ether, tetrahydrofuran, CrC 8 -Carboxylic acids, ethyl acetate and mixtures thereof.
• one or more precursor compounds are dissolved in a mixture of acetic acid, ethanol and water.
• this contains Mixture 30 to 75 wt .-% acetic acid, 30 to 75 wt .-% ethanol and 0 to 20 wt .-% water.
• zirconium (IV) acetylacetonate, hexamethyldisiloxane, tin 2-ethylhexanoate, platinum acetylacetonate, lanthanum (II) acetylacetonate and cesium acetate are dissolved in a mixture of acetic acid, ethanol and water.
• Preferred apolar solvents are toluene, xylene, n-heptane, n-pentane, octane, isooctane, cyclohexane, methyl, ethyl or butyl acetate or mixtures thereof. Hydrocarbons or mixtures of hydrocarbons with 5 to 15 carbon atoms are also suitable. Especially preferred is xylene.
• Zr (IV) propylate, hexamethyldisiloxane, tin 2-ethylhexanoate, platinum acetylacetonate and lanthanum (III) acetylacetonate are dissolved in xylene.
• the present invention also provides the catalyst particles obtainable by the process according to the invention. These preferably have a specific surface area of 36 to 70 m 2 / g.
• the catalyst particles have the following percentage composition: 30 to 99.5 wt .-% Zr0 2 and 0.5 to 25 wt .-% Si0 2 as a carrier, 0.1 to 1 wt .-% Pt, 0 , 1 to 10 wt .-% Sn, La and / or Cs, based on the mass of the carrier, wherein at least Sn and La or Cs are included.
• the present invention also relates to the use of the catalyst particles as hydrogenation catalysts or dehydrogenation catalysts.
• Alkanes such as butane and propane, but also ethylbenzene are preferably dehydrated.
• catalysts of the invention for the dehydrogenation of propane to propene.
• the invention is further illustrated by the following examples.
• HMDSO Hexamethyldisiloxane
• the solvent is HoAc: EtOH: H 2 O in the mass ratio 4.6 to 4.6 to 1.
• the acetic acid-ethanol mixture is freshly prepared. This dissolves the precursor compounds for Sn, Cs, La, Si, Pt and Zr.
• composition of the polar solutions of the precursor compounds for Examples 1, 2, 3, 9 and 10 can be found in Table 1.
• Table 1 Compositions of solutions of precursor compounds for polar
• Table 2 Compositions of solutions of precursor compounds for apolar
• the solution containing the precursor compounds was fed by means of a piston pump via a two-fluid nozzle and sprayed with an appropriate amount of air.
• a support flame was partially used from an ethylene-air mixture, which was metered via a ring burner located around the nozzle.
• the pressure drop was kept constant at 1, 1 bar.
• Table 3 summarizes the flame synthesis conditions.
• GLMR gas to liquid mass ratio.
• a baghouse filter was used to separate the particles. To clean these filters, the filter bags were subjected to 5 bar pressure surges of nitrogen.
• Particle characterization was performed by X-ray diffractometry (XRD) and BET measurement and elemental analysis. The crystallite size of the formed catalyst particles using the solution of the precursor compounds 3 and 4 are shown in Table 4. Table 4: X-ray powder diffractometry for the characterization of Zr0 2
• the BET surface area was investigated as a function of the combustion chamber temperature.
• the solutions containing the precursor compounds were compared with regard to their solvent (acetic acid versus xylene). There was no clear trend in the acetic acid mixtures.
• the xylene approaches showed an increasing BET surface area with increasing temperature, which can be attributed to a shorter residence time, which limits particle growth.
• the propane dehydrogenation was carried out at approx. 600 ° C. (Rivers at 20 ml Cat volume, see table 5 for mass): 21 Nl / h total gas (20 Nl / h propane, 1 Nl / h nitrogen as internal standard), 5 g / h water.
• the regeneration is carried out at 400 ° C as follows: 2 hours 21 Nl / h N 2 + 4 Nl / h air; 2 hours 25 Nl / h air; 1 hour 25 Nl / h of hydrogen.
• the support of the reference catalyst from the hydrothermal synthesis (Zr0 2 ) followed by spray drying consists of 95% Zr0 2 and 5% Si0 2 .
• the active / promoter metals are 0.5% Pt, 1% Sn, 3% La, 0.5% Cs and 0.2% K and were wet-chemically impregnated by the procedure according to EP 1 074 301, Example 4 applied the carrier.
• Figure 1 shows activities and selectivities of the flame-synthesized catalysts ( ⁇ Example 13, ⁇ Example 17) and the reference catalyst (-) in the autothermal dehydrogenation of propane to propene.
• the catalyst ( ⁇ ) only the carrier was prepared by pyrolysis and the carrier was then wet-chemically impregnated as in the case of the reference catalyst.
• the abscissa shows the time in hours, the ordinate shows turnover (40 to 50%) and selectivities (> 80%). It shows a comparable performance of the three catalysts.
• the reference catalyst has lower initial selectivities. However, over the experimental cycles of a few weeks, it adapts to the catalysts according to the invention. Thus, the flame-synthesized catalyst behaves like an aged catalyst, which was prepared conventionally wet-chemically.

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• 2012
  • 2012-01-23 JP JP2013549929A patent/JP2014511258A/ja not_active Withdrawn
  • 2012-01-23 EP EP12739695.0A patent/EP2667969A1/de not_active Withdrawn
  • 2012-01-23 KR KR1020137022257A patent/KR20140010050A/ko not_active Withdrawn
  • 2012-01-23 WO PCT/IB2012/050302 patent/WO2012101566A1/de not_active Ceased
  • 2012-01-23 CN CN2012800086590A patent/CN103379958A/zh active Pending
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